J Polym Environ
DOI 10.1007/s10924-012-0475-9
ORIGINAL PAPER
The Potential of Chicken Eggshell Waste as a Bio-filler Filled
Epoxidized Natural Rubber (ENR) Composite and its Properties
Punyanich Intharapat · Aroon Kongnoo ·
Kavichat Kateungngan
© Springer Science+Business Media, LLC 2012
Abstract Eggshell calcium carbonate (ECC) and egg-
shell calcium carbonate treated with high temperature
(ECC-600) were prepared from chicken eggshell waste.
ECC was obtained by crushing eggshell waste, eliminating
membranes and followed by sieving. In the case of ECC-
600, ECC powder was additionally heated at 600 °C for
2 h. Both were used to promote as fillers compared to that
of commercial light-precipitated calcium carbonate (com-
mercial CaCO3) with various loading levels (i.e., 0, 25, 50
and 75 phr) in epoxidized natural rubber containing 25 mol
% of epoxide group (ENR-25). Among the three types of
fillers (i.e., ECC, ECC-600 and commercial CaCO3), ECC
filled materials showed superior vulcanization characteris-
tics by the increasing of maximum torque (MH) and cure
rate index (CRI) with the reducing of cure time (tc90) and
scorch time (ts2). The highest tensile properties as well as
P. Intharapat (&)
Environmental Biotechnology Research Unit, Prince of Songkla
University, Hatyai, Songkhla 90112, Thailand
e-mail: punyanich.i@psu.ac.th
P. Intharapat
Center of Excellence for Environmental and Hazardous Waste
Management (EHWM), Bangkok 10330, Thailand
P. Intharapat · A. Kongnoo
Faculty of Environmental Management, Prince of Songkla
University, Hatyai, Songkhla 90112, Thailand
K. Kateungngan
Department of Chemistry, Faculty of Science, Ubon Ratchathani
University, Ubon Ratchathani 34190, Thailand
A. Kongnoo
The Joint Graduate School of Energy and Environment (JGSEE),
King Mongkut’s University of Technology Thonburi,
Bangkok 10140, Thailand
the lowest tension set value were also observed. Morpho-
logical property revealed that ECC was greater interfacial
adhesion than those of others. In addition, dynamic
mechanical properties of vulcanizates containing ECC,
storage modulus (E´) was the highest and glass transition
temperature (Tg) shifted toward high temperature.
Increasing of loading levels of any fillers affected the
increase of MH and CRI with reducing of tc90 and ts2.
However, tensile properties decreased with increasing filler
content but it did not affect Tg shifting except for a series
of vulcanizates containing ECC.
Keywords Eggshell · Epoxidized natural rubber ·
Calcium carbonate · Bio-filler
Introduction
Recently, using waste materials in polymeric products have
taken an important role for environmental and economic
concerns. Some of these wastes such as tyre rubber waste
[1–5], rice husk ash [6, 7], fly ash [8, 9], bagasse [10, 11]
and paper sludge [12] have been added in polymer matrix
in order to produce new functional composite materials.
Eggshell is one of the significant solid wastes produced
mainly from food processing and manufacturing plants
[13]. Traditionally, most eggshell waste is discarded
without further processing by sending to landfills at a high
handling cost. For economic concerns, eggshell waste can
be used to convert biomaterials into commercial products
and creates new values from these waste materials. It is
known that eggshell waste contains lots of valuable organic
and inorganic components which can be used in many
applications such as cosmetics, biomedical, ceramics,
coating pigments as well as filler in thermoplastics [14–20].
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Using chicken eggshell powder as a filler in polymeric
materials especially natural rubber and its derivatives have
been done in a few studies. The chemical composition (by
weight) of eggshell has been reported to consist mainly of a
mineral part ([95 %) of calcite crystals and a pervading
organic matrix (1–3.5 % of the remaining material) [21, 22].
Thus, it can be considered a good source of CaCO3. Since
calcium carbonate is by far an important and the most
widely filler used because of its whiteness, low abrasion,
availability in wide-size ranges and low cost [23]. Conse-
quently, it is not only a filler added to reduce costs but today
it is the material engineering for the different requirements
of modern products [24, 25]. Several works reported the use
of eggshell as a filler in polymeric materials. Dakhel [26]
has investigated vulcanization characteristic and mechani-
cal property of acrylonitrile butadiene rubber (NBR),
natural rubber (NR) and styrene butadiene rubber (SBR)
compounds filled with eggshell powder. The optimum cure
time of all compounds decreased and mechanical properties
were improved. Saeb et al. [27] have shown that the
incorporation of eggshell filled SBR compounds exhibited
increase of almost all of the mechanical properties with no
considerable effect on curing time. However, in the case of
using eggshell as a filler in epoxidized natural rubber (ENR)
has not been previously reported. The exploration of using
modified NR such as ENR is conducted to extend the useful
properties in a variety of applications and to improve
inferior properties of NR. It is because of the epoxide
groups which involved the addition of oxygen atom to a
proportion of the carbon–carbon double bonds, thereby
converting them to an oxirane (or epoxide) ring. This
resulted in a systematic increasing in the polarity and glass
transition temperature. Since these increases are reflected in
the superior properties over NR including the increase in
non-polar chemical resistance (i.e., hydrocarbon oils), high
thermal stability, good damping, wet grip performance and
the decrease in air permeability while retaining the inherent
high strength of NR. Furthermore, the presence of epoxide
group in ENR was also found to be effective in causing
specific interaction with a second polymer in polymer
blending system and improved compatibility by increasing
in filler reinforcement of composite materials [28–30].
This study involved the preparation of a bio-calcium
carbonate from chicken eggshell waste for use as a filler in
ENR-25 compounds. Influences of preparation and loading
levels of eggshell calcium carbonate (ECC) compared with
commercial calcium carbonate (commercial CaCO3) were
investigated on vulcanization characteristics, swelling
behavior, mechanical properties, morphological property,
and dynamic mechanical properties. The point of application
of chicken eggshell waste was to explore possibility using
eggshell as a replacement part of commercial calcium car-
bonate filler by determine the proper type and loading level
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J Polym Environ
of ECC in elastomeric compounds which is not only to
improve mechanical properties and other important proper-
ties but also to reduce environmental pollutions.
Experimental
Materials
ENR-25 used as a polymer matrix was manufactured by
Muang Mai Guthrie Co., Ltd. (Phuket, Thailand). This
grade of material contains 25 mol% of epoxide group with
mooney viscosity 57 (ML 1 + 4, 100 °C). The zinc oxide
(ZnO) and stearic acid used as activators, manufactured by
Global Chemical Co., Ltd. (Samutprakarn, Thailand) and
Imperial Chemical Co., Ltd. (Pathumthani, Thailand),
respectively. The sulphur and tetramethyl thiuramdisulfide
(TMTD) used as a vulcanizing agent and an accelerator
were manufactured by Ajax Chemical Co., Ltd. (Samut-
prakarn, Thailand). The chicken eggshell wastes used as a
bio-filler were obtained from the canteen located in Ubon
Rachathani University, Thailand. The commercial light-
precipitated calcium carbonate (CaCO3) used as a filler was
obtained from Kij Paiboon Chemical Ltd. (Thailand).
Preparation of Calcium Carbonate from Chicken
Eggshell Waste
There are two procedures used to prepare calcium carbonate
particles from eggshell waste in order to obtain eggshell
calcium carbonate (ECC) and eggshell calcium carbonate
treated with high temperature (ECC-600). The outline of the
preparation of both fillers from chicken eggshell waste was
shown in Fig. 1 and described below.
Eggshell Calcium Carbonate (ECC)
Thousand grams of chicken eggshell waste were washed
with water several times and roughly crushed in small
pieces. ECC was prepared by the mechanical stirring of
1,000 g of crushed eggshell waste in a 5,000 ml size vessel
containing 3,000 ml of water for 48 h at an agitation speed
of 100 rpm. This caused lighter eggshell membranes to
float up while the heavier calcium carbonate settled down
at the bottom of the vessel. After that, the vessel was
overflowed with water to separate the membranes. The
crude eggshell calcium carbonate pieces were then col-
lected and dried at 100 °C over night. After that, it was
ground and sieved in a 400 mesh sieve to obtain fine
eggshell calcium carbonate (ECC) particles and left in a
desiccator.
J Polym Environ
Fig. 1 Outline for preparation of eggshell calcium carbonate (ECC)
and eggshell calcium carbonate treated with high temperature (ECC-
600)
Eggshell Calcium Carbonate Treated with High
Temperature (ECC-600)
The preparation of ECC-600 was carried out by heated
ECC powder obtained from above at 600 °C for 2 h. It was
then collected and left in a desiccator.
Characterization of Fillers Properties
X-ray diffraction (XRD) patterns obtained at room tem-
perature by D8 Advance, Bruker ASX, using Cu Kα
radiation (λ = 1.5406 Å) in a range of 2θ = 10–80° at a
scan rate of 0.05 s−1 were used to identify the crystalline
phase of fillers. The surface area of fillers was determined
by the Brunauer–Emmett–Teller (BET) method on a ASAP
2020 surface area, and pore size was characterized by
mercury porosimetry (Model Pore-Sizer 9320, Micromer-
itics, USA). The pH was determined by the procedure
described in ASTM D1512. The chemical composition of
CaCO3 and metal oxides (i.e., MgO, SrO, Na2O, K2O and
P2O) of all fillers were examined by X-ray fluorescence
spectrometer (XRF) model S4 Explorer (Brukeraxs, Ger-
many). The nitrogen content in chicken eggshell waste was
determined by kjeldahl method. The presence of functional
groups on the surfaces of the fillers was verified by Fourier
Transform Infrared spectroscopy (FT-IR) recorded on an
Omnic ESP Magna-IR 560 spectrometer at a resolution of
4 cm−1, in the spectral range of 4,000–500 cm−1. The
samples (0.2 mg) were ground with 50 mg dry potassium
bromide (KBr) in a mortar and then pressed to form thin
disks. The disks were dried in an oven at 100 °C for 24 h
prior to the analysis. The thermal degradation behavior of
fillers used was determined by Thermogravimetric analysis
(TGA) technique using TGA Q500, TA instrument, (New
Castle, USA). The samples (10 mg) were first placed in a
platinum pan under nitrogen atmosphere. The test was then
performed with a heating rate of 10 °C min−1 within a
temperature range of 50–1,000 °C.
Preparation and Testing of ENR-25 Compounds
The compositions of the ENR-25 formulations with addi-
tives (i.e., activators, accelerator and antioxidant), curing
agent (i.e., sulphur) and fillers were given in Table 1. A
laboratory two roll mill sized (160 9 320 mm) according to
ASTM designation D3184 was used for compound mixing
and maintained at 70 ± 5 °C. At the end of the mixing
cycle, the materials were collected and conditioned at a
temperature of 25 ± 1 °C for 24 h before cure assessment
(i.e., minimum torque (ML), maximum torque (MH), torque
difference (MH–ML), scorch time (ts2), cure time (tc90) and
cure rate index (CRI)) using Moving die rheometer
(RheoTech MD+, Tech Pro, Inc., Cuyahoya Falls, USA) at
160 °C. The amplitude of the oscillation was set at 0.5 of
arc at a frequency of 1.7 Hz, according to ISO 6502.
Tensile testing of the samples was performed at 25 ± 2 °C
at a crosshead speed of 500 mm min−1. The instrument used
was a Hounsfield Tensometer, model H 10 KS manufactured
by the Hounsfield Test Equipment Co., Ltd., UK. The
dumbbell-shaped specimens, 2 mm thick, were prepared by
fabrication of rubber compounds at 160 °C into a sheet by a
compression molding machine using cure time according to
results obtained from a vulcanization test. Tensile properties
(ASTM D412) were measured along the grain direction,
whereas tear strength (ASTM D624, Die C) was measured
perpendicular to the grain direction. Tension set at 100 %
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Table 1 Formulation and mixing schedule for preparation of ENR-25 mean particle sizes of commercial CaCO3 were slightly
compounds smaller than ECC and ECC-600, respectively. However,
Material Quantity Mixing the BET surface area of ECC particles was considerably
(phr) time (min) higher than that of commercial CaCO3. Some of this
increased surface area of ECC particles over than com-
ENR-25 100 5
mercial CaCO3 particles was attributed to the presence of
ZnO 5 2
roughness of the external surface corresponding to mor-
Stearic acid 1 1
phological details in Fig. 5. Furthermore, it was due to
Variable fillers (i.e., CaCO3, 0, 25, 50, 75 5
ECC and ECC-600) surface area related to porosity which the eggshell con-
Wingstay L 1 1
tained a significant amount of gas exchange pores [31, 32].
TBBS 1 1.5
This could be the advantage of ECC particles according to
higher specific surface area although particle size was
Sulphur 2 1.5
larger than commercial CaCO3. Considering ECC-600, it
was not only the largest particle size but also the particle
elongation was determined at room temperature (25 ± 2 °C) with the lowest surface area. This may be attributed to the
according to ASTM D412. Hardness of the samples was also sintering at surface contact particles from burning ECC
measured using a Shore A type according to ASTM D2240. particles at high temperature (i.e., 600 °C) causing the
A scanning electron microscope (SEM), model JSM-5800 trend of agglomeration and accordingly increased particle
LV (Jeol, Tokyo, Japan) was used to characterize morpho- sizes with decreased BET surface area. It has also been
logical properties of fillers filled ENR-25 vulcanizate in found that all types of fillers provided the alkaline pH. This
various proportions of fillers for the dispersion and interfa- can be explained by the presence of impurities, particularly
cial adhesion observations. The samples were first metal oxides [33]. The determination of organic fraction in
cryogenically cracked in liquid nitrogen to create new sur- form of proteins as represented by nitrogen content corre-
faces. They were then dried in a hot air oven at 40 °C for 48 h sponding to the kjeldahl method showed that ECC
and sputter-coated with gold before examining by a scanning consisted of a small amount of nitrogen (i.e., 3.05 wt%)
electron microscope at magnification 500 and 5,000 times. whereas nitrogen content was not found in the commercial
The dynamic mechanical thermal analysis (DMTA) was CaCO3 and ECC-600. This can be postulated that only
conducted using rectangular samples with dimensions ECC is composed of protein in particles. XRD patterns of
35 9 11 9 2.7 mm on a DMTA machine of the TA ECC, ECC-600 and commercial CaCO3 were presented in
instrument. Storage modulus (E′), loss tangent (tan δ) and Fig. 2. It was found that their XRD patterns showed similar
glass transition temperature (Tg) were examined at fre- crystalline peaks of ECC, ECC-600 and commercial
quencies of 1 Hz in the temperature range of −100 to 50 °C. CaCO3, and exhibited obviously a significant peak around
30° (2θ), which was characteristic of crystalline calcite that
indicated as hkl (104) [34]. Hence, this was identified as a
Results and Discussion pure calcite crystal structure of all samples according to the
JCPDS file No. 05-0586. It was in good agreement with
Characterization of ECC, ECC-600 and Commercial those of previous works [35, 36]. FTIR spectroscopy was
CaCO3 used to seek an evidence of the functional groups in dif-
ferent fillers, as IR spectra shown in Fig. 3. It can be seen
The characteristics of ECC, ECC-600 and commercial that various absorption bands were observed the significant
CaCO3 were summarized in Table 2. It can be seen that the peak of intensity at around 1,557–1,455, 880–871 and

Table 2 Characteristics of ECC, ECC-600 particles and commercial CaCO3 fillers

Sample Average BET surface Median Density pH Composition (weight %)
particle area (m2/g) pore size (μm) (g/cm3)
size (μm) Calcium Metal oxidesa Nitrogen
carbonatea (i.e., MgO, SrO, contentb
Na2O, K2O, Fe2O3)

Commercial CaCO3 15 2.112 0.1 2.70 9.5 99.78 0.92 –

ECC 26 2.532 1.1 2.59 9.7 96 .41 1.45 3.05
ECC-600 29 1.902 1.3 2.47 9.5 96.56 1.38 –
a
Determined by XRF technique
b
Determined by Kjeldahl method

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Fig. 2 XRD patterns of commercial CaCO3, ECC and ECC-600
Fig. 3 FT-IR spectra of commercial CaCO3, ECC and ECC-600
712 cm−1 assigned to the CO3 vibrations in fillers (i.e.,
CaCO3, ECC and ECC-600). In addition, the absorption
band around 2,515–2,512 cm−1 was associated with HCO3.
However, IR spectra of ECC showed the peak at
3,415 cm−1 assigned for N–H [18, 37]. This indicated the
present amine functionality of the organic part existed in
ECC powder according to proteins in the calcified layers
[29, 38], while the appearance of the characteristic peaks at
3,415 cm−1 disappeared in commercial CaCO3 and
ECC-600. This result indicated the effectiveness of puri-
fying ECC-600 particles after high temperature treatment
at 600 °C. Consequently, the IR characteristics of CO3 and
HCO3 functions as observed in both ECC and ECC-600
were comparable to commercial CaCO3 because of the
occurrence of calcium carbonate composition. The thermal
stability behaviors of commercial CaCO3, ECC and ECC-
600 samples can be described by TGA thermograms in a
relation of weight losses at the temperature range from 50
to 1,000 °C as shown in Fig. 4. It can be seen that the
degradation of commercial CaCO3 and ECC-600 occurred
in a single step, where the decrease started at 630 °C and
ended at 850 °C with a weight loss of 60 %. This degra-
dation was assigned to the burning of CaCO3 to produce
calcium oxide (CaO) and carbon dioxide (CO2). In a case
Fig. 4 TG curves of commercial CaCO3, ECC and ECC-600
of ECC, it showed double degradation steps. In the first
step, the degradation temperature occurred at 250 °C and
ended at 380 °C with a weight loss of 3.1 %. It belonged to
the slight decomposition of organic fraction (protein) into
small molecules CO, CO2 [39]. This indicated that ECC
still contained a little portion of organic part, which cor-
responded with the FT-IR result and nitrogen content. At
the second step, the decomposition began at 630 °C and
ended at 850 °C, which was similar to those of commercial
CaCO3 and ECC-600, with a weight loss of 58 %. It was
because of the loss of CO2 from the chicken eggshell
carbonate, and the sample into CaO with no loss of weight
at 900 °C. Fillers surface of commercial CaCO3, ECC and
ECC-600 were revealed in Fig. 5. It can be seen that
commercial CaCO3 particle had a smooth surface over
ECC particle which was covered with rough places pro-
viding a higher specific surface area of ECC. In the case of
ECC-600 particle, a porous structure was observed on the
surface. This was influenced by gaseous product that
resulted from the decomposition of organic matter during
burning [31]. It was therefore able to diffuse throughout
solid material surface as a result of generating pores.
Furthermore, it can be noted that there was not eggshell
membrane presented on the particle surfaces of ECC and
ECC-600. This indicated that the eggshell membrane was
completely removed.
Vulcanization Characteristics
The effect of different fillers filled ENR-25 compounds on
vulcanized properties was determined by relationship of
torque and time. The MDR cure curves were shown in
Fig. 6 and the data was summarized in Table 3. It can be
clearly seen that there was significant improvement in
the vulcanization characteristics as evidenced from the
increase in the maximum torque (MH) obtained for the
fillers containing compounds (i.e., ECC, ECC-600 and
commercial CaCO3) compared to that of the unfilled
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Fig. 5 SEM micrographs of fillers surface of a commercial CaCO3, b
ECC and c ECC-600 particles
compound. The effect of different fillers filled compounds
on MH and torque difference (MH–ML) was described in
Table 3. It can be seen that the differences of torque which
related to the level of modulus of the rubber vulcanizates
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Fig. 6 Cure curves of ENR-25 compounds containing commercial
CaCO3, ECC and ECC-600 with various loading levels of 0, 25, 50
and 75 phr
were observed in different fillers. For ECC filled com-
pound, it showed the MH value which was higher than
ECC-600 and commercial CaCO3, respectively. A possible
explanation of this observation was given by the presence
of the organic part (i.e., protein) and inorganic parts (i.e.,
metal oxide) of eggshells that participated in the curing
process, and participation of these elements led to con-
siderable increase in curing rate and modulus [33, 40].
Another relevant reason could be that the reactivity of the
amino groups of the proteins linked at the surface of ECC
particles was able to react with the oxirane rings of ENR-
25 through physical hydrogen bonding and chemical
covalent bonds as shown in Fig. 9. As a consequence, the
increasing loading level of ECC particles led to the
increasing of torque values by the formation of strong
chemical and physical bonds. In case of ECC-600 and
commercial CaCO3, they had similar torque values due to
their physical properties being almost comparable. The
scorch time (ts2) or time to incipient cure and optimum cure
time (tc90) were determined from the increase of the min-
imum torque (ML) value by two units and the time at the
torque which reached to 90 % of MH, respectively. The ts2
and tc90 of ENR-25 compounds with and without fillers
showed that the ts2 and tc90 of compounds decreased with
incorporation of fillers compared to that of unfilled com-
pounds. This may be attributed to these fillers (i.e.,
commercial CaCO3, ECC and ECC-600) provided typical
chemical alkalinity of calcium carbonate fillers category
leading to the speed up of curing reactivity. Therefore,
increased levels of filler loading caused reducing of ts2 and
tc90 (i.e., faster cure). Among commercial CaCO3, ECC and
ECC-600 at a fixed fillers loading, ECC containing com-
pounds offered the shortest ts2 and tc90. Whereas, ECC-600
showed ts2 and tc90 slightly different to those of commer-
cial CaCO3. This was possible due to the presence of
proteins remaining in ECC which could participate and act
J Polym Environ

Table 3 Curing characteristics of ENR-25 compounds containing commercial CaCO3, ECC and ECC-600 with various loading levels
Sample ML (dN m) MH (dN m) MH–ML Cure time Scorch time CRI (1/min)
(dN m) tc90 (min) (ts2) (min)

ENR-25 1.21 14.87 13.66 1.90 0.98 108.69

Commercial CaCO3 25 phr 1.27 19.31 18.04 1.86 0.97 112.23
Commercial CaCO3 50 phr 1.44 22.68 21.24 1.58 0.80 128.11
Commercial CaCO3 75 phr 3.23 25.81 22.58 0.99 0.28 140.69
ECC 25 phr 1.30 19.86 18.56 1.50 0.83 147.29
ECC 50 phr 1.49 24.15 22.66 1.25 0.58 150.08
ECC 75 phr 1.27 29.16 27.89 1.08 0.42 152.14
ECC-600 25 phr 1.38 17.34 15.96 1.69 0.95 135.40
ECC-600 50 phr 1.41 23.02 21.61 1.39 0.67 139.20
ECC-600 75 phr 1.63 27.00 25.37 1.01 0.33 146.45

as activators [41–43] in the vulcanization process leading

to enhancement of cure reaction. For cure rate index (CRI),
which is a measure of the rate of the cure reaction based on
the difference between tc90 and ts2, the result showed that
ENR-25 without fillers had a lower CRI than ENR-25
containing fillers. In addition, CRI increased with increased
filler content for all types due to increasing the presence of
chemical alkalinity. Among the three types of fillers
incorporated at the same loading level in the ENR-25
formulations, the CRI of ECC containing formulation was
higher than the CRIs of ECC-600 and commercial CaCO3.
It can be explained by the synergism of organic (i.e.,
protein) and metal oxide remnant (i.e., MgO) in ECC,
which was capable of supporting the activation of the cure Fig. 7 Tensile strength of ENR-25 vulcanizates filled commercial
CaCO3, ECC and ECC-600 with various loading levels of 0, 25, 50
reaction [6, 33]. Formulations incorporating ECC-600 and 75 phr
compared to that loading with commercial CaCO3 also
showed a slightly higher increase of CRI. One can suppose
that the content of metal oxide in the filler (Table 1) can act
on the rate of vulcanization since the vulcanized processing
depended on the contents of metal oxides (i.e., MgO, ZnO).
This led to enhance the cure rate, and reduce the scorch
time and cure time of the vulcanization system. This can be
explained by the same reasons of scorch time and cure
time.

Mechanical Properties

Figures 7 and 8 represented the tensile strength and tear

strength of vulcanizates, respectively. It can be seen that,
among the three types of fillers, the vulcanizate contained
ECC was higher than commercial CaCO3 and ECC-600,
respectively. This can be explained by ECC particles
possessing a high BET surface area, which provided better
interfacial adhesion between the filler and rubber matrix. In
addition, the reinforcement effect by ECC particles was
found to be higher than that of commercial CaCO3. It was
probably expected that the strong interfacial adhesion for
Fig. 8 Tear strength of ENR-25 vulcanizates filled commercial
CaCO3, ECC and ECC-600 with various loading levels of 0, 25, 50
and 75 phr
ECC filled ENR-25 by the possible formation of covalent
chemical bonds between reactivity of the amine at the
interface of ECC fillers towards the oxirane rings in the

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Fig. 9 Schematic representation of the possible formation site for
interaction between ENR-25 and ECC particle
epoxidized rubber chains [44], and also the reinforcement
of hydrogen bonding occurred between the specific affinity
of polar epoxide groups in rubber chains and the small
amount of polar amine (–NH2) groups in protein (i.e.,
polypeptide) that existed on the filler surfaces. A proposed
possible site for interaction between ENR-25 and ECC
particles was shown in Fig. 9. Furthermore, surface
roughness of ECC particles can also affect the interfacial
adhesion between ECC particle and ENR matrix. Since
surface with roughness can yield better wetting resulting in
more contact interface area and a interfacial adhesion.
Therefore, ECC particles provided better load transfer from
the matrix to the filler and reduced of stress concentration
at the cracked tips compared to that of commercial CaCO3
and ECC-600. Considering the tensile strength of each
filler type filled ENR-25, it was found that the increasing of
fillers loading in the rubber matrix resulted in the
decreasing in both tensile strength and tear strength. This
was due to the dilution effect [45] and higher filler content
may lead to larger interfacial area with filler loading across
the matrix which caused increasing and promoting the
stress in the continuous phase. The elongation at break of
ECC filled vulcanizates was slightly lower than ECC-600
and commercial CaCO3, respectively, as shown in Fig. 10a.
Furthermore, the increasing of filler loading regardless of
any types of filler caused a decreasing of elongation at
break as expected. This decreasing was due to the pro-
motion of brittleness and rigidity with filler loading
resulting in a reduction of elasticity of the rubber vulca-
nizates. Variation of hardness of commercial CaCO3, ECC
and ECC-600 filled ENR-25 with different loading levels
of filler was represented in Fig. 10b. It can be seen that the
addition of fillers in any types was not significantly dif-
ferent. At a given filler, hardness increased with increasing
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filler content. This indicated that the hardness property of
the vulcanizate was typically dominated by the filler
loading. It was due to the presence of rigid calcium car-
bonate particles (i.e., commercial CaCO3, ECC and ECC-
600) that caused increasing brittleness and the trend of
hardness. For the rubber elasticity of the rubber vulcaniz-
ates, it can be estimated by the tension set property as
shown in Fig. 10c. Among the three types of fillers, it can
be seen that the incorporation of ECC in rubber exhibited
the lowest value of the tension set while the vulcanizate
containing ECC-600 gave the highest tension set value, and
commercial CaCO3 filled vulcanizate had an intermediate
value. This was evidence of the highest interfacial adhesion
of ECC and hence the strongest elasticity of the composite.
Furthermore, at given filler types, it was also seen that the
increasing of filler loading from 0 to 75 phr caused the
increasing of tension set from 12 to 13.5 %, 12 to 16.5 %
and 12 to 17 % of ECC, ECC-600 and commercial CaCO3
filled rubber, respectively. This behavior may infer that the
fillers could restrict and act as a barrier to the mobility of
recovery rubber chains resulting in a reduction of elasticity
of the vulcanizates. The effect of different filler types with
various loading levels filled ENR-25 vulcanizates on mass
swell of IRM 903 oil was shown in Fig. 10d. It can be seen
that, at a given filler loading, ECC filled rubber provided
the highest oil resistance followed by commercial CaCO3
and ECC-600, respectively. This was due to the interface
between filler and rubber matrix became stronger as a
result of the highest specific surface area of ECC particles.
Hence, the lower free volume at the interface restricted oil
molecules to enter and to be trapped. In addition, increas-
ing oil resistance (or the decreasing degree of swelling)
was observed when increasing filler content in any type of
filler. It can be demonstrated that fillers acted as liquid
insulators and barriers to prevent oil penetrating toward
rubber.
Morphological Property
Morphological characteristics of rubber composites coming
from commercial CaCO3, ECC and ECC-600 filled ENR-
25 with various fillers loading were investigated by cryo-
genic cracks. The micrographs, given in Fig. 11, showed a
two-phase morphology where the white spots representing
filler particles were dispersed in the ENR-25 matrix (black
area). It can be seen that ECC particles and commercial
CaCO3 particles exhibited phases that were more uniformly
dispersed. On the other hand, ECC-600 revealed the
poorest dispersion. This can be attributed to the different
effectiveness of surface area and particle size. Since ECC-
600 had the smallest surface area and largest particle size
resulting in the weakest filler-polymer interface adhesion.
Whereas, a high surface area with a small particle size led
J Polym Environ
Fig. 10 Properties of ENR-25 vulcanizates filled commercial CaCO3, ECC and ECC-600 with various loading levels of 0, 25, 50 and 75 phr on
a elongation at break, b hardness, c tension set and d swelling resistance
to good interfacial adhesion between filler particles and
rubber matrix as a consequence of better dispersion and
homogeneity. The well-dispersed ECC and commercial
CaCO3 particles could correlate positively to the trend of
mechanical properties (i.e., tensile strength, tear strength,
tension set and hardness), while ECC-600 had poor filler
dispersion yielding reducing the filler-rubber interactions
and consequently decreasing the ability of the fillers to
restrain gross deformation of the rubber matrix. Hence the
mechanical properties of vulcanizate containing ECC-600
were lower than other fillers. This trend was more signifi-
cantly detected in the vulcanizates with high magnification
(i.e., 5,000 times) of three types of filler filled ENR-25 at a
fixed filler loading level of 75 phr as shown in Fig. 12. It
was clearly seen that the interface area between dispersed
ECC particles and ENR-25 matrix closed each other while
commercial CaCO3 and ECC-600 particles provided more
interface space area between these fillers and the ENR-25
matrix. This could confirm the interaction between ECC
particles and ENR-25 through the organic part and the
surface roughness of particles, which was stronger than the
commercial CaCO3 and ECC-600 particles, resulting in
greater wettability at the direct interface between filler and
elastomer.
Dynamic Mechanical Properties
From DMTA thermograms in terms of a relationship
between storage modulus (E′) and temperature as shown in
Fig. 13 and the data was summarized in Table 4, it can be
seen that E′ of the filler filled rubber in the low temperature
region (i.e., glassy state) was greater than that of unfilled
rubber. This was due to the incorporation of more rigid
filler particles into rubber causing the material behavior to
be more like a solid, hence an increase of E′ values. With a
further increasing of temperature, E′ of filled and unfilled
rubber dropped suddenly after approximate −60 to −30 °C
for different compounds as a result of the glass transition
phenomenon by a part of polymer chains moving. More-
over, it can be noted that ECC filled rubber was slightly
higher E′ in glass transition state. This may be attributed
to the interfacial adhesion between ECC particles and
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 J Polym Environ

Fig. 11 SEM micrographs of ENR-25 filled with a commercial level of 75 phr, e ECC-600 at loading level of 50 phr and f ECC-600
CaCO3 at loading level of 50 phr, b commercial CaCO3 at loading at loading level of 75 phr (magnification 9500)
level of 75 phr, c ECC at loading level of 50 phr, d ECC at loading

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J Polym Environ

Fig. 12 SEM micrographs of ENR-25 filled with a commercial CaCO3, b ECC and c ECC-600 at loading level of 75 phr (magnification 95000)

ENR-25 through the organic part on the surface particles

which created stronger polymer-filler adhesion than com-
mercial CaCO3 and ECC-600 particles, respectively. This
observation revealed that the surface activity (i.e., rubber-
filler interaction) and the surface area are the most
important factors which may impart energy storage yield-
ing the decreased energy loss and lower viscous
characteristics. Above −20 °C, the values of E′ became
almost constant. Therefore, increasing of temperature
caused decreasing trend of E′ until stabilized and constant
within the elastic region of the material. Also, E′ depended
on fillers loading in glassy, glass transition and rubbery
state as shown in Fig. 14. For the ECC example, it was Fig. 13 Storage modulus (E′) of unfilled ENR-25 vulcanizate and
found that E′ increased with filler incorporation compared different fillers (i.e., commercial CaCO3, ECC and ECC-600) filled
to that of unfilled ENR-25. In addition, increasing of fillers ENR-25 vulcanizates at a fixed loading level of 75 phr

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 J Polym Environ

Table 4 DMTA data of ENR-25 composites containing commercial CaCO3, ECC and ECC-600 with various loading levels
Sample code Storage modulus (E′) (9103 MPa) Maximum tan Tg ( °C)
δ (tan δmax)
Types of filler −80 °C −50 °C 25 °C

Without filler 2.51 1.17 0.03 2.70 −48.2

Commercial CaCO3 25 phr 2.55 1.18 0.06 3.05 −48.2
Commercial CaCO3 50 phr 2.64 1.25 0.12 3.31 −48.2
Commercial CaCO3 75 phr 2.68 1.30 0.30 3.40 −48.0
ECC 25 phr 2.57 1.20 0.06 2.81 −48.1
ECC 50 phr 2.66 1.28 0.14 3.00 −47.5
ECC 75 phr 2.72 1.41 0.31 3.26 −46.4
ECC-600 25 phr 2.52 1.17 0.05 3.23 −48.2
ECC-600 50 phr 2.61 1.19 0.12 3.48 −48.2
ECC-600 75 phr 2.65 1.20 0.29 3.72 −48.3

loading from 25 phr up to 75 phr caused gradually

increasing trend of E′. This behavior was similarly
observed in all filler types. It might be attributed to the
increasing of stiffness in rubber with increasing of filler
loading resulting in strict and limited mobility of polymer
chains. This behavior agreed with several previous works
that the incorporation of solid filler into a polymer matrix
increased E′ of the polymer [46–48]. Considerably above
the glass transition region (i.e., 25 °C), it was also seen that
E′ increased slightly upon increasing the filler content
regardless of filler types after increasing temperature. This
proposed that the rubber vulcanizates became tougher,
harder and more thermal stability with increasing filler
loading. Figure 15 showed the temperature dependence on Fig. 14 Storage modulus (E′) of ENR-25 vulcanizates filled with
tan δ (loss tangent or damping factor) of the commercial various loading levels of ECC particles
CaCO3, ECC and ECC-600 filled ENR-25 at a fixed filler
loading of 75 phr compared with the unfilled ENR-25. At
the temperatures of tan δ peak, which are ascribed to the
glass transition temperatures (Tg), it can be seen that the
unfilled vulcanizate showed a peak of tan δ at a Tg
approximately −48.2 °C as described in Table 4. In case of
fillers filled vulcanizates as shown in Fig. 15, it was
observed that the peak temperature of tan δ curve of ECC
filled rubber was slightly shifted to a higher temperature
range (i.e., −46.4 °C). Whereas, the Tg’s of commercial
CaCO3 and ECC-600 filled ENR-25 were not obviously
affected (i.e., −48.0 and −48.3 °C, respectively). The Tg
shifting of ECC filled ENR-25 can be explained by pow-
erful interfacial adhesion between ECC and ENR-25 Fig. 15 Tan δ of unfilled ENR-25 vulcanizate and different fillers
(i.e., commercial CaCO3, ECC and ECC-600) filled ENR-25 vulca-
phases causing restriction in the mobility of molecular nizates at a fixed loading level of 75 phr
chains in the vicinity of ECC particles more than CaCO3
and ECC-600 particles, respectively. These may confirm with increasing fillers loading as shown in Fig. 16 and was
the stronger interfacial interaction of ECC, which was listed in Table 4. Furthermore, the heat dissipation corre-
affected through organic part and possessing high surface sponding to the peak intensity (tan δmax) increased with
area comparison with that lacking of organic composition filler loading. The increasing of tan δmax can be explained
and low surface area of commercial CaCO3 and ECC-600 by a decreasing of polymer-filler interface leading to
particles. At a fixed filler type (i.e., ECC), Tg also increased increasing energy loss and increasing in damping

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J Polym Environ
Fig. 16 Tan δ of ENR-25 vulcanizates filled with various loading
levels of ECC particles
properties of the material. Variations of tan δ peak by the
increase of filler were found the same trend in the series of
commercial CaCO3 and ECC-600.
Conclusion
Eggshell calcium carbonate (ECC) and eggshell calcium
carbonate treated with high temperature (ECC-600) pre-
pared from chicken eggshell waste were applied to use as
fillers comparing with commercial CaCO3 in ENR-25. The
chemical characteristic of ECC composed of 96.41 %
CaCO3 and 3.05 % organic part speculated to be mainly
proteins. In case of ECC-600 and commercial CaCO3, they
mainly consisted of 96.56 and 99.78 % CaCO3, respec-
tively. The cure characteristics, mechanical, morphological
and dynamic mechanical properties were examined as a
function of different types of fillers and fillers loading (i.e.,
0, 25, 50 and 75 phr). For cure characteristics, the scorch
time (ts2) and cure time (tc90) were the shortest while
minimum torque (ML), maximum torque (MH) and cure
rate index (CRI) were the highest in the presence of ECC
particles in compounds. These may be attributed to the
existing protein in the particles that acted as an activator in
the vulcanization process leading to enhancement of the
cure reaction. In addition, ts2, and tc90 decreased and an
increase in ML, MH and CRI was observed with increasing
filler loading regardless of fillers used. Tensile strength,
tear strength, hardness, tension set and swelling resistance
of ECC filled ENR-25 were also greater than commercial
CaCO3 and ECC-600 due to better filler-rubber interaction
through high surface area with roughness surface and the
organic part of ECC particles. However, increasing loading
levels of whatever filler caused decreasing of tensile
strength, tear strength and elongation at break with
increasing of hardness, tension set and swelling. The good
dispersion and superior interfacial adhesion can be clearly
seen in ECC over other types. It was expected that the
larger surface area of ECC and a polar amine (-NH2)
groups in protein existed in particles hence greater the
interaction and stronger the interfacial adhesion between
the filler and rubber matrix. The ECC-600 had the poorest
dispersion and the weakest filler-polymer interface adhe-
sion due to the smallest surface area of ECC-600 giving a
weaker interaction at interface, and commercial CaCO3 had
an intermediate. Dynamic mechanical behavior of ENR-25
composites with different fillers showed that E′ or stiffness
of ECC filled vulcanizates can be enhanced by improving
the surface area and surface reactivity of fillers, filler dis-
persion and filler-rubber interaction. The tan δ values of the
composite increased with incorporation of any fillers,
indicating higher heat dissipation than unfilled ENR-25.
Among the three types of fillers, ECC filled ENR-25 was
the lowest tan δ. It was noted that the greater interfacial
adhesion caused lower energy dissipation than those with
poorer interfacial adhesion. In addition, tan δ increased
with increasing filler loading in all types of fillers. The Tg
of vulcanizate containing ECC was shifted to a higher
temperature with increasing fillers content but it did not
cause severe effect on commercial CaCO3 and ECC-600.
These observations indicated that mobility of polymer
chains decreased in the presence of ECC.
Acknowledgments The authors are deeply grateful to Dr. Daniel
Derouet for valuable suggestions given. We are also thankful to the
faculty of Science, Ubonrachathani University for access to facilities
throughout the work.
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